Color couplers for color photography



llnited States Patent COLOR COUPLERS FOR COLOR PHOTOGRAPHY Arthur HenriDe Cat, Mortsel-Antwerp, and Rapha'e'l Karel Van Poucke, Mechlin,Belgium, assignors to Gevaert Photo-Producten N.V., Mortsel, Belgium, 2Belgian company No Drawing. Filed Apr. 3, 1956, Ser. No. 575,718 Claimspriority, application Great Britain Apr. '5, 1955 2 Claims. (Cl.260-507) This invention relates to a process for producing photographiccolor images by color development, to color couplers for use in suchprocess, and to the preparation of such color couplers.

It is known to produce color photographic images by color development.The color couplers needed for this purpose are preferably incorporatedin the photographic emulsion layers or in colloid layers located in thevicinity thereof. In order to prevent wandering of these conplers out oftheir initial layer into another layer, they are usually loaded by asubstituent such as a chain of several carbon atoms. Besides thissubstituent, other substituents which render the coupler water-solubleare usually introduced. Sulpho groups in particular are efiective inthis respect.

As couplers for yellow, the acylacetarylides have been used in practice.As acylacetarylides sulphonated in their arylide part, only the acetylacetarylides have been obtained by allowing diketene to react withsulphonated aniline derivatives. Corresponding sulphonatedaroylacetarylides have not been obtained, due to the lack of a suitablemethod.

An object of the present invention is a method for preparingaroyl-acetarylides sulphonated in the arylide part. A further object isa class of new sulphonated aroyl-acetarylides. Another object is aprocess for the production of a colored photographic image by the use ofthese aroyl-acetarylides. Still a further object is a light-sensitivephotographic material containing such aroylacetarylides.

Now we have found a method for preparing such aroyl-acetarylidessulphonated in the arylide part and it has been found that suchcompounds are good couplers. In comparison with similar couplers, theyare very soluble and are indifierent to silver halide emul- SIOIIS.

According to the present invention, a reducible silver salt image isdeveloped with a primary amino aromatic developing agent in the presenceof an aroyl-acetarylide sulphonated in its arylide part wherein thehydrogen atoms of the metehylene group may be replaced by substituentswhich readily split oil on color development.

Further according to the present invention, such compounds are preparedby condensing an aroylacetic ester with a compound of the formula NH-aryl-SO F, and by hydrolyzing the rsulting sulphofluoride into thecorresponding sulphonic acid or ester. The aryl group of the ester or ofthe sulphofluoride may contain a group able to render the coupler fastto difiusion. Alternatively, the aryl group of the ester may contain anitro group which after condensation may be reduced to an amino group,wherein a group rendering fast to diffusion may be introduced Withoutdifliculty.

Compounds of the formula NH -aryl-SO F may be obtained in differentWays.

Aromatic compounds may be treated with fluorosulphonic acid. Steinkopf(I. prakt. Chem. (2) 117 (1927) 1-82) has nitrated two sulphofluorides,obtained in this way, into m-Nitro-benzene sulphofluoride, andp-Methyl-m-nitro-benzene sulphofiuon'de.

According to W. Davies and J. Dick (J. Chem. Soc. (1931) 2104-09),compounds of the formula aryl-S0 01 may be treated with potassiumfluoride. have prepared:

o-Nitro-benzene-sulphofluoride, M.P. 60 C.,p-Nitro-benzene-sulphofiuoride, M.P. C.,p-Chloro-rn-nitro-benzene-sulphofluoride, M.P. 54 C.,

and

In this way we p Dimethylamino m nitro -benzene -sulphofluoride,

M.P. 64 C.

The above six nitro-sulphofluorides have been converted into thecorresponding amino compounds by reducing a 25% alcoholic solution ofthe nitro-sulphofluoride by means of Raney nickel at 40-400 C. and undera hydrogen pressure of 10-100 atm. After elimination of the Raneynickel, the filtrate is either distilled or evaporated until the aminecrystallizes. In this way we have prepared.

m-Aminobenzenesulphofluoride, B.P. 161 C./ 14

o-Amino-benzene-sulphofluoride, M.P. 62 C.

p-Amino-benzenc-sulphofiuoride, M.P. 68-70 C.,

p-Chlorom-amino-benzene-sulphofluoride, M.P. 69 C.,

p-Dimethyl-amino-m-amino benzene-sulphofluoride, M.P.

p-Methyl-m-amino-benzene-sulphofluoride, M.P. 93 C.

Potassium fluoride may also be allowed to react with acetyl-aminoarylene sulphochlorides. The resultingacetylamino-arylene-sulphofiuorides may be de-acylated by means of HClin alcohol. In this way we have prepared:

p-Methoxy-amino-benzene-sulphofluoride, M.P. 62 C.,

2-Methoxy-5-amino-benzene-sulphofluoride, M.P. 74 C.,

and

2 5 dimethoxy 3 amino benzene sulphofluoride,

M.P. 132 C.

CH (CH COCl (myristoyl-chloride),p-myristoyl-amino-m-nitro-benzenesulphofluoride, M.P. 64 C. (fromacetonitrile), is obtained. Reducing the latter with Raney nickel indioxane at 40-50 C. and under a hydrogen pressure ofi 10-50 atm.,eliminating the nickel and evaporating the filtrate until the productcrystallizes by cooling, yieldsp-myristoyl-amino-m-amino-benzene-sulphofluoride, M.P. 122 C.

Condensation of these sulphofluorides with beta-keto esters may be donein the usual way by refluxing the two compounds in toluene or xylene,evaporating the latter after condensation, and recrystallizing theproduct.

The following compounds were prepared in this way:

rn-(p-Hexadecyl-oxy-benzoyl-acetyl-amino) -benzenesulphofluoride, M.P.112 C.,

'p-(p-Hexadeeyl-oxy-benzoylracetyl amino) -benzene-sulphofluoride, M.P.135 C.,

p-Methoxy-m- (p-heXadecyl-oxy-benzoyl acetyl amino)-benzene-sulphofluoride, M.P. 156 C.,

p-Methyl-rn- (p-hexadecyl-oxy-benzoyl-acetylamino) -benzene-sulphofluoride, M.P. 135 C.,

p-(p-Dodecyl-oXy-benzoyl-acetyl-amino)-benzene-sulphofluoride, M.P. 144C.,

m- [p-(p-Isooctyl phenoxy ethoxy) benzoyl]acetylamino-benzene-sulphofluoride, M.P. 148 C.,

p-Myristoyl amino-m-benzoyl-acetyl-amino-benzene sulphofiuoride,M.P..160 C.,-

3-(p-hexadecyl-oxy-benzoyl-acetyl amino) 6methoxybenzene-sulphofluoride, M.P. 105 C.,

3-(p-hexadecyl-oxy-benzoyl acetyl-amino)-4-chloro benzenesulphofluoride,M.P. 132 C.,

3-(p-hexadecyl-oxy-benzoyl-acetyl-amino) -4-methylbenzene-sulphofluoride, M.P. 139 C.,

3 (p-heXadecyl-oxy-benzoylacetylamino) 2-5-dimethoxybenzene-sulphofluoride, M.P. 120 C.,

m-(p-I-Iexadecyl-oXy-naphthoyl-acetyl amino) benzenesulphofluoride, M.P.98-99 C.,

m- (4-HeXadecyl-oXy-3-5-dichloro-benzoyl-acetyl-amino)benzene-sulphofluoride, M.P. 132l35 C.,

m-(a-Hexadccyl-oxy-fi-naphthoyl-acetyl-amino)-benzenesulpbofluoride,M.P. 90-92 C.,

m-(p-Hexadecyl-oXy-m-methoXy-benzoyl-acetyl amino)-benzene-sulphofiuoride, M.P. 9799 C., and

p- (Hexadecyl-oxy-m-methoxy-b enzoyl-acetyl-amino) -b en-'zene-sulphofluorideJMP. 115116 C.

By condensing m-amino-benzene-sulphofluoride with m-nitro benzoyl-aceticacid ethyl ester and reducing the resulting product with Raney nickel inethyl alcohol at 6080 C. and under a hydrogen pressure of 80-100 atm.,m-[m-amino-benzoyl-acetyl-aminol benzene sulphofluoride was obtained.From the latter were obtained, by condensation with palmito-yl chlorideand with alpha-hexa-decyl succinic anhydride:

m- (m-palmitoyl-amino-benzoyl-acetyl amino) benzenesulphofluoride, M.P.96-98 C., and

m[m(Alpha-hexadecyl-succinyl amino)benzoylacetyllbenzene-sulphofluoride, M.P; 180 C.

In order to convert the sulphofluorides into the correspending sulphonicacids, they are first dissolved in acetone or aqueous dioxane andtreated at 60 C. with an aqueous solution of sodium hydroxide. Aftercooling, the sodium salt of the coupler crystallizes out, or isprecipitated by the addition of salt. These sodium salts arerecrystallized and may easily be. dissolved in water or in a mixture ofwater and alcohol for addition to a silver halide emulsion or to acolloid which will form a layer adjacent to a silver halide emulsionlayer or separated therefrom by a water-permeable colloid layer.

As primary aromatic amino developing agents may be used mono-, diandtri-amino compounds; as monoamino developers may be mentioned aminophenols and amino cresols, their halogen derivatives, and also aminonaphthols.

wherein R represents an aryl radical selected from the group consistingof alkoxyphenyl, alkoXy naphthyl, dialkoxy phenyl, dichloro alkoxyphenyl, isooctyl phenoxy ethoxy phenyl, nitrophenyl, and acylaminophenyl, R" represents a monocyclic arylene radical of the. benzeneseries, selected from the group consisting of phenylene,chlorophenylene, dialkyl amino phenylene, alkyl phenylene, alkoxyphenylene, dialkoxyphenylene, and acylaminophenylene, and Me representsan alkali metal atom, comprising condensing an 'aroyl acetic ester ofthe following formula:

wherein R represents a lower alkyl group, with a compound of the formulaH N-R'SO F, and hydrolyzing V the resulting compound in the presence ofan alkali metal hydroxide.

2. A sulphonated aroyl-acetarylide of the following structure:

wherein R represents an aryl radical selected from the group consistingof alkoxyphenyl, alkoXy naphthyl, dialkoxy phenyl, dichloro alkoxyphenyl, isooctyl phenoxy ethoxy phenyl, nitrophenyl, and acylaminophenyl, R represents a monocyclic arylene radical of the benzene series,selected from the group consisting of phenylene, chlorophenylene,dialkyl amino phenylene, alkyl phenylene, alkoxy phenylene,dialkoxyphenylene, and acylaminophenylene, and Me represents an alkalimetal atom, said sulphonated aroyl acetarylide being prepared bycondensing an aroyl acetic ester of the following formula: V

RCO'CH -COOR wherein R" represents a lower alkyl group, with a compoundof the formula H NR'-SO F, and hydrolyzing the resulting compound in thepresence of an alkali metal hydroxide. 7

References Cited in the file of this patent UNITED STATES PATENTS1,971,409 Henle et a1. Aug. 28, 1934 2,083,962 Petitcolas June 15, 19372,303,928 Froehlick et al. Dec. 1, 1942 2,312,040 Kendall et al Feb. 23,1943 2,748,164. Dodson May 29, 1956

2. A SULPHONATED AROYL-ACETARYLIDE OF THE FOLLOWING STRUCTURE: